US4526722A - Manufacture of diacyloxy aromatic compounds - Google Patents
Manufacture of diacyloxy aromatic compounds Download PDFInfo
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- US4526722A US4526722A US06/486,150 US48615083A US4526722A US 4526722 A US4526722 A US 4526722A US 48615083 A US48615083 A US 48615083A US 4526722 A US4526722 A US 4526722A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 150000001491 aromatic compounds Chemical class 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 45
- 239000011541 reaction mixture Substances 0.000 claims description 16
- -1 palladium carboxylate Chemical class 0.000 claims description 11
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 10
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 7
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000001463 antimony compounds Chemical class 0.000 claims description 3
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- ITAMCOCNZJPJDF-UHFFFAOYSA-N 1-(6-aminopurin-9-yl)propan-2-yloxymethyl-phenoxyphosphinic acid Chemical compound C1=NC2=C(N)N=CN=C2N1CC(C)OCP(O)(=O)OC1=CC=CC=C1 ITAMCOCNZJPJDF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims 1
- 150000002941 palladium compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 10
- 239000011651 chromium Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 37
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 5
- ZBZSVGXZAPNCSY-UHFFFAOYSA-N phenyl octanoate Chemical compound CCCCCCCC(=O)OC1=CC=CC=C1 ZBZSVGXZAPNCSY-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- SUAOWWVNMRJABO-UHFFFAOYSA-N naphthalen-1-yl octanoate Chemical compound C1=CC=C2C(OC(=O)CCCCCCC)=CC=CC2=C1 SUAOWWVNMRJABO-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
Definitions
- the present invention provides a process for preparing aryl diesters from aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, fluorene, biphenyl, terphenyls, and the like, which comprises reacting a mixture of the aromatic hydrocarbon, for instance naphthalene, a carboxylic acid, and molecular oxygen in the liquid phase in the presence of a catalyst consisting essentially of palladium or a compound of palladium, a compound of antimony and a compound of at least one member selected from the group consisting of an alkali metal, chromium, zinc, antimony and tin.
- aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, fluorene, biphenyl, terphenyls, and the like.
- U.S. Pat. No. 3,542,852 discloses the preparation of hydroxy aromatic compounds by reaction of an aromatic compound and oxygen in the presence of a catalyst composed of iron, a noble metal or a compound of either in the presence of a nitrate ion and a carboxylic acid. More recently, the preparation of phenyl esters and phenols by the reaction of benzene, molecular oxygen and a lower aliphatic carboxylic acid in the presence of a catalyst composed of a Group VIII metal (U.S. Pat. No. 3,642,873) or a compound of such metal (U.S. Pat. No. 3,651,127) have been disclosed. Similarly, variations in this type of reaction have been disclosed in U.S. Pat. Nos.
- U.S. Pat. No. 3,959,354 concludes that liquid phase reactions of this type because of problems of catalyst elution, etc., are disadvantageous for an industrial process.
- U.S. Pat. No. 3,772,383 describes a liquid phase reaction using a very complex catalyst system which includes the use of nitric acid and a lower aliphatic carboxylic acid.
- U.S. Pat. No. 3,644,486 discusses the production of acylation products of condensed aromatic compounds in the liquid phase with oxygen and a saturated carboxylic acid in the presence of a noble metal or compound thereof.
- the catalysts useful in my process are preferably composed of palladium metal or compounds of palladium and usually a palladium carboxylate in conjunction with an antimony compound and a compound of at least one member selected from the group consisting of an alkali metal (preferably potassium), chromium, zinc, manganese and tin.
- the catalysts useful in the process of this invention may be used alone or may be supported on a carrier or carriers. Suitable carriers include silica, alumina, carbon, quartz, pumice, diatomaceous earth, and the like and others which are well known in the art.
- Carboxylic acids useful in our invention are the monocarboxylic acids which correspond to the formula RCOOH wherein R is a hydrocarbon group having from 1 to 19 carbon atoms. Some carboxylic acid anhydride can be included in the reaction if desired.
- a mixture of naphthalene, the carboxylic acid and optionally an inert solvent such as n-heptane is contacted in the liquid phase with molecular oxygen and a catalyst at a reaction temperature in the range of from about 100° to 300° C. and preferably at from 140° to 200° C. and at from 1 to 100 and preferably 1 to 10 atmospheres but most preferably at or near atmospheric pressure.
- the molecular oxygen can be oxygen per se, or any gaseous mixture containing oxygen and other inert gases such as nitrogen, argon, carbon dioxide, etc.
- molecular oxygen used in the process of this invention can be in the form of air for convenience.
- the catalyst can be a mixture of palladium diacetate, antimony triacetate and at least one member selected from the group consisting of potassium acetate, chromium acetate, zinc acetate, manganese acetate and tin acetate.
- the molar ratio of Pd:Sb:other metal should be in the range of 1:50:20 to 1:0.1: 0.1 and preferably in the range 1:20:10 to 1:0.2:0.2.
- the water formed is removed continuously as it forms usually by azeotropic distillation with an excess of reactant or with an inert solvent which can be present in the reaction mixture.
- Inert solvents which can be included in the reaction mixture used in the process of this invention include linear hydrocarbons having the formula C n H 2n+2 wherein n is from 4 to 14 such as heptane, pentane, hexane, octanes and the like, cyclic hydrocarbons having the formula C n H 2n wherein n is from 4 to 14, and linear and cyclic aliphatic ethers.
- the starting material can be either an aromatic hydrocarbon or a mono-acyloxy aromatic hydrocarbon. In either case the product will be the diacyloxy aromatic hydrocarbon.
- the product is primarily 1,5-diacyloxy naphthalene
- alpha-acyloxy naphthalene is used as starting material
- the product is again primarily 1,5-diacyloxy naphthalene but a shorter reaction time is needed to convert the alpha-acyloxy naphthalene.
- part of this invention relates to a process for the conversion of monoacyloxy aromatic hydrocarbons to diacyloxy aromatic hydrocarbons.
- a reactor equipped with a mechanical stirrer, a thermometer with temperature controller and a Dean-Stark type condenser was charged with 0.349 g (1.5 m mols) of Pd(OAc) 2 , 0.45 g (1.5 m mol) of Sb(OAc) 3 , 0.15 g (1.5 m mols) of KOAc, 43 g (300 m mols) of octanoic acid, 10 g (78 m mols) of naphthalene and 10 ml of n-heptane.
- the Dean-Stark type collector was also filled with n-heptane. The reaction mixture was stirred vigorously and brought to the reaction temperature of 170° C.
- Example 1 The procedure of Example 1 was followed except that the catalyst was composed of 3 m mols each of the acetate salts of palladium antimony and chromium and 5 g (18.5 m mols) of alpha-naphthyl octanoate were used in place of naphthalene.
- the reaction time was 4 hours and analysis of the reaction mixture showed that about 50% of the alpha-naphthyl octanoate was converted to dioctanoxy naphthalene (mainly 1,5-isomer).
- Example 1 The procedure of Example 1 was followed except that 1.5 m mols of Sn(OAc) 2 were used instead of KOAc. The reaction was carried out for about 10 hours and produced 6 m mols of the diacyloxy naphthalene along with 54 m mols of the mono acyloxy naphthalene.
- Example 1 The procedure of Example 1 was followed using 0.31 g (1.4 m mols) of Pd(OAc) 2 , 0.42 g (1.4 m mols) of Sb(OAc) 3 , 0.14 g (1.4 m mols) of KOAc, 82 g (568 m mols) of octanoic acid and 10 g (128 m mols) of benzene.
- the reaction was carried out at 170° C. for 20 hours.
- GLC analysis of the reaction mixture showed the formation of 80 m mols of phenyl octanoate and 5 m mols of dioctanoxy benzene.
- the selectivity of the diacyloxy product was about 75% ortho (catechol precursor) and about 20% meta (resorcinol precurser) and 5% para (hydroquinone precursor).
- Example 1 The procedure of Example 1 was followed using 0.11 g (0.5 m mol) of Pd(OAc) 2 , 0.15 g (0.5 m mol) of Sb(OAc) 3 , 0.12 g (0.5 m mol) of Cr(OAc) 3 .H 2 O, 308 m mols of octanoic acid and 5 g (64 m mols) of benzene.
- the reaction was carried out at 182 + 2° C. and additional benzene was introduced into the reaction mixture occasionally to maintain a steady reflux. The reaction time was five hours.
- the final reaction mixture was found by GLC analysis to contain 11% by weight of phenyl octanoate and 2% by weight of phenyl dioctanoate (73% ortho, 21% meta and 6% para).
- Example 1 The procedure of Example 1 was followed using 3 m mols of Pd(OAc) 2 , 3 m mols of Sb(OAc) 3 , 3 m mols of Cr(OAc) 2 , 360 m mols of octanoic acid, 45.5 m mols of phenyl octanoate and 10 ml of n heptane. Heptane was also included in the Dean Stark tube. The reaction was conducted at 180 + 2° C. for 5 hours under a constant flow of oxygen at about 50 cc/min. GLC analysis of the product showed a 23% conversion to phenyl octanoate with 10 m mols of dioctanoxy benzene (74% ortho, 20% meta and 6% para) being formed.
- Example 6 The procedure of Example 6 was followed using 3 m mols of Mn(OAc) 2 instead of the Cr(OAc) 3 . The reaction was carried out for 6 hours during which 20% of the phenyl octanoate was converted giving 8.5 m mols of dioctanoxy benzene.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process is described for the manufacture of diacyloxy aromatic hydrocarbons by the liquid phase reaction of an aromatic hydrocarbon or a monoacyloxy aromatic hydrocarbon with molecular oxygen in the presence of a carboxylic acid over a catalyst composed of a compound of palladium, a compound of antimony and a compound of at least one member selected from the group consisting of an alkali metal, chromium, zinc, antimony and tin wherein the water formed in the reaction is rapidly and continuously removed from the reaction as it forms.
Description
This invention is an improvement over the processes described and claimed in copending U.S. patent applications of Ser. No. 416,809, of Anil B. Goel, filed Sept. 13, 1982, now U.S. Pat. No. 4,464,303, and Ser. No. 441,360, of Anil B. Goel and Peter E. Throckmorton, filed Nov. 15, 1982, U.S. Pat. No. 4,465,633.
1. Field of the Invention
The present invention provides a process for preparing aryl diesters from aromatic hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, fluorene, biphenyl, terphenyls, and the like, which comprises reacting a mixture of the aromatic hydrocarbon, for instance naphthalene, a carboxylic acid, and molecular oxygen in the liquid phase in the presence of a catalyst consisting essentially of palladium or a compound of palladium, a compound of antimony and a compound of at least one member selected from the group consisting of an alkali metal, chromium, zinc, antimony and tin.
2. Description of the Prior Art
The manufacture of phenol by direct oxidation of benzene with oxygen is known. There are, for instance, thermal processes which are performed at very high temperatures in which phenol formed is susceptible to further oxidation so that considerable loss of yield occurs as is disclosed in U.S. Pat. No. 2,223,383. In the presence of catalysts, the oxidation can be carried out at somewhat lower temperatures as in U.S. Pat. No. 3,133,122, but the reactions have been plagued by low conversions and excessive production of unwanted by-products as discussed in U.S. Pat. No. 2,392,875.
It has already been proposed to make phenyl acetate and biphenyl from benzene and acetic acid in the liquid phase in the presence of palladium acetate and without added molecular oxygen by a stoichiometric reaction in Chem. and Ind., Mar. 12, 1966, Page 457.
U.S. Pat. No. 3,542,852 discloses the preparation of hydroxy aromatic compounds by reaction of an aromatic compound and oxygen in the presence of a catalyst composed of iron, a noble metal or a compound of either in the presence of a nitrate ion and a carboxylic acid. More recently, the preparation of phenyl esters and phenols by the reaction of benzene, molecular oxygen and a lower aliphatic carboxylic acid in the presence of a catalyst composed of a Group VIII metal (U.S. Pat. No. 3,642,873) or a compound of such metal (U.S. Pat. No. 3,651,127) have been disclosed. Similarly, variations in this type of reaction have been disclosed in U.S. Pat. Nos. 3,646,111; 3,651,101; 3,772,383; 3,959,352 and 3,959,354. U.S. Pat. No. 3,959,354 concludes that liquid phase reactions of this type because of problems of catalyst elution, etc., are disadvantageous for an industrial process. U.S. Pat. No. 3,772,383 describes a liquid phase reaction using a very complex catalyst system which includes the use of nitric acid and a lower aliphatic carboxylic acid. U.S. Pat. No. 3,644,486 discusses the production of acylation products of condensed aromatic compounds in the liquid phase with oxygen and a saturated carboxylic acid in the presence of a noble metal or compound thereof.
Generally speaking, these prior art processes deal for the most part with vapor phase oxidation reactions, or liquid phase reactions in which all the reactants (except oxygen in some instances) are initially included in the reaction mixtures. Moreover, in general the prior art catalytic processes have produced very low conversions, usually less than 10%, with low selectivity to the desired monophenyl ester, and phenol or phenolic materials are often a primary product of the oxidation reaction. None of the prior art processes show the production of diacyloxy products nor do any of them show the continuous removal of water from the reaction mixture as it forms.
I have discovered an oxidation process for the transformation of naphthalene, benzene, and similar aromatic hydrocarbons, molecular oxygen and a carboxylic acid to the corresponding aromatic dicarboxylate in high conversions and selectivities to the desired product. The process involves the use of a liquid phase and a catalyst composed of palladium or a compound of palladium with a compound of antimony and at least one compound of a member selected from the group consisting of an alkali metal (such as potassium), chromium, zinc, manganese and tin. I have also discovered that high conversions and high selectivity to the diacyloxy aromatic compounds are continuous removal of water from the reaction mixture as it forms during the entire course of the reaction. If water, which is a by-product of the reaction, is allowed to remain in the reaction mixture it can cause hydrolysis of the diacyloxy aromatic compound to form phenolic materials which in turn can cause deactivation of the catalyst.
The catalysts useful in my process are preferably composed of palladium metal or compounds of palladium and usually a palladium carboxylate in conjunction with an antimony compound and a compound of at least one member selected from the group consisting of an alkali metal (preferably potassium), chromium, zinc, manganese and tin. The catalysts useful in the process of this invention may be used alone or may be supported on a carrier or carriers. Suitable carriers include silica, alumina, carbon, quartz, pumice, diatomaceous earth, and the like and others which are well known in the art.
Carboxylic acids useful in our invention are the monocarboxylic acids which correspond to the formula RCOOH wherein R is a hydrocarbon group having from 1 to 19 carbon atoms. Some carboxylic acid anhydride can be included in the reaction if desired.
Our liquid phase oxidation process produces in the case of naphthalene or alpha-acyloxy naphthalene conversions of 10% or greater with selectivities in the order of 100% to the diacyloxy naphthalene. The diacyloxy products of this process can be readily converted to the dihydroxy aromatic compound by hydrolysis or pyrolysis.
In a typical reaction in accordance with this invention a mixture of naphthalene, the carboxylic acid and optionally an inert solvent such as n-heptane is contacted in the liquid phase with molecular oxygen and a catalyst at a reaction temperature in the range of from about 100° to 300° C. and preferably at from 140° to 200° C. and at from 1 to 100 and preferably 1 to 10 atmospheres but most preferably at or near atmospheric pressure. The molecular oxygen can be oxygen per se, or any gaseous mixture containing oxygen and other inert gases such as nitrogen, argon, carbon dioxide, etc. For instance, molecular oxygen used in the process of this invention can be in the form of air for convenience.
The catalyst can be a mixture of palladium diacetate, antimony triacetate and at least one member selected from the group consisting of potassium acetate, chromium acetate, zinc acetate, manganese acetate and tin acetate. The molar ratio of Pd:Sb:other metal should be in the range of 1:50:20 to 1:0.1: 0.1 and preferably in the range 1:20:10 to 1:0.2:0.2.
During the process of this invention the water formed is removed continuously as it forms usually by azeotropic distillation with an excess of reactant or with an inert solvent which can be present in the reaction mixture. Inert solvents which can be included in the reaction mixture used in the process of this invention include linear hydrocarbons having the formula Cn H2n+2 wherein n is from 4 to 14 such as heptane, pentane, hexane, octanes and the like, cyclic hydrocarbons having the formula Cn H2n wherein n is from 4 to 14, and linear and cyclic aliphatic ethers.
Because essentially no phenolic compounds are produced in the process of this invention, it is believed that catalyst activity is maintained for long periods of time under continued use. The rapid removal of water from the reaction mixture is probably at least partly responsible for the absence of phenolic materials in the reaction product. The presence of phenolic materials in the reaction products of prior art processes is believed to be at least partly reponsible for catalyst fouling, short catalyst life and low conversion obtained.
In the process of this invention the starting material can be either an aromatic hydrocarbon or a mono-acyloxy aromatic hydrocarbon. In either case the product will be the diacyloxy aromatic hydrocarbon. When naphthalene is used as the starting material, the product is primarily 1,5-diacyloxy naphthalene, when alpha-acyloxy naphthalene is used as starting material, the product is again primarily 1,5-diacyloxy naphthalene but a shorter reaction time is needed to convert the alpha-acyloxy naphthalene. Similarly, when benzene is used as starting material in the process of this invention the product is a mixture of ortho, para and meta diacyloxy benzene and when monoacyloxy benzene is used as starting material the same diacyloxy benzenes are obtained in a shorter reaction time. Thus, part of this invention relates to a process for the conversion of monoacyloxy aromatic hydrocarbons to diacyloxy aromatic hydrocarbons.
This invention is further illustrated in the following examples.
A reactor equipped with a mechanical stirrer, a thermometer with temperature controller and a Dean-Stark type condenser was charged with 0.349 g (1.5 m mols) of Pd(OAc)2, 0.45 g (1.5 m mol) of Sb(OAc)3, 0.15 g (1.5 m mols) of KOAc, 43 g (300 m mols) of octanoic acid, 10 g (78 m mols) of naphthalene and 10 ml of n-heptane. The Dean-Stark type collector was also filled with n-heptane. The reaction mixture was stirred vigorously and brought to the reaction temperature of 170° C. A continuous flow of oxygen at the rate of 50 cc/min was passed through the reaction mixture during the reaction period of 5 hours. About 1.6 ml of water was collected in the Dean-Stark collector during the reaction. The final reaction mixture was found by GLC analysis to contain 40 m mols of monoacyloxy-naphthalene (97% of alpha-naphthyl ester, 3% beta-naphthyl ester) and 24 m mols of diacyloxy-naphthalene (mainly the 1,5-isomer). The reaction was continued for an additional hour and at the end of this time GLC analysis of the reaction mixture showed essentially 100% conversion of the naphthalene and the formation of 28 m mols of diacyloxy naphthalene. This means that 50 m mols of naphthalene were converted to mono acyloxy naphthalene.
The procedure of Example 1 was followed except that the catalyst was composed of 3 m mols each of the acetate salts of palladium antimony and chromium and 5 g (18.5 m mols) of alpha-naphthyl octanoate were used in place of naphthalene. The reaction time was 4 hours and analysis of the reaction mixture showed that about 50% of the alpha-naphthyl octanoate was converted to dioctanoxy naphthalene (mainly 1,5-isomer).
The procedure of Example 1 was followed except that 1.5 m mols of Sn(OAc)2 were used instead of KOAc. The reaction was carried out for about 10 hours and produced 6 m mols of the diacyloxy naphthalene along with 54 m mols of the mono acyloxy naphthalene.
The procedure of Example 1 was followed using 0.31 g (1.4 m mols) of Pd(OAc)2, 0.42 g (1.4 m mols) of Sb(OAc)3, 0.14 g (1.4 m mols) of KOAc, 82 g (568 m mols) of octanoic acid and 10 g (128 m mols) of benzene. The reaction was carried out at 170° C. for 20 hours. GLC analysis of the reaction mixture showed the formation of 80 m mols of phenyl octanoate and 5 m mols of dioctanoxy benzene. The selectivity of the diacyloxy product was about 75% ortho (catechol precursor) and about 20% meta (resorcinol precurser) and 5% para (hydroquinone precursor).
The procedure of Example 1 was followed using 0.11 g (0.5 m mol) of Pd(OAc)2, 0.15 g (0.5 m mol) of Sb(OAc)3, 0.12 g (0.5 m mol) of Cr(OAc)3.H2 O, 308 m mols of octanoic acid and 5 g (64 m mols) of benzene. The reaction was carried out at 182+ 2° C. and additional benzene was introduced into the reaction mixture occasionally to maintain a steady reflux. The reaction time was five hours. The final reaction mixture was found by GLC analysis to contain 11% by weight of phenyl octanoate and 2% by weight of phenyl dioctanoate (73% ortho, 21% meta and 6% para). A catalytic turnover number (mols of product produced per mol of catalyst) of about 55 was observed.
The procedure of Example 1 was followed using 3 m mols of Pd(OAc)2, 3 m mols of Sb(OAc)3, 3 m mols of Cr(OAc)2, 360 m mols of octanoic acid, 45.5 m mols of phenyl octanoate and 10 ml of n heptane. Heptane was also included in the Dean Stark tube. The reaction was conducted at 180+ 2° C. for 5 hours under a constant flow of oxygen at about 50 cc/min. GLC analysis of the product showed a 23% conversion to phenyl octanoate with 10 m mols of dioctanoxy benzene (74% ortho, 20% meta and 6% para) being formed.
The procedure of Example 6 was followed using 3 m mols of Mn(OAc)2 instead of the Cr(OAc)3. The reaction was carried out for 6 hours during which 20% of the phenyl octanoate was converted giving 8.5 m mols of dioctanoxy benzene.
Claims (6)
1. A process for the manufacture of diaryl esters consisting essentially of contacting a reaction mixture of benzene or a monophenyl ester, a carboxylic acid and molecular oxygen in the liquid phase at a temperature in the range of from 100° to 300° C. with a catalyst composed of palladium or a compound of palladium, an antimony compound and a compound of at least one member selected from the group consisting of an alkali metal and tin wherein the molar ratio of Pd:Sb:other metals is in the range of 1:50:20 to 1:0.1:0.1.
2. The process of claim 1 wherein the carboxylic acid has the formula RCOOH wherein R is a hydrocarbon group having from 1 to 19 carbon atoms.
3. The process of claim 2 wherein the palladium compound is a palladium carboxylate.
4. The process of claim 3 wherein the antimony compound is an antimony carboxylate.
5. The process of claim 4 wherein the catalyst is composed of palladium acetate, antimony acetate and potassium acetate and the carboxylic acid is octanoic acid.
6. The process of claim 4 wherein the catalyst is composed of palladium acetate, antimony acetate and tin acetate.
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